Certificate of correction



Patented Mar. 28, 1933 UNITED STATES PATENT OFFICE OBIN D. CUNNINGHAM, OF INDIANAPOLIS, INDIANA, ASSIGNOB TO PETER C. REILLY,

- OF INDIANAPOLIS, INDIANA PROCESS OF ORE FLOTA'IION AND FLOTATION REAGENT No Drawing.

This invention relates to the concentration of materials, particularly metalliferous materials by the froth flotation operation, and has for its object the provision for certain improvements involving the use of a certain class of organic substances as collecting agents in the concentration of such materials as ores and minerals. The invention embraces both the product and the method of making the same, as well as the use of the product in the froth flotation operation.

The present invention is based on the discov'ery that certain unsaturated fatty acid compounds such as, for example, oleic acid dissolved in or mixed with a phenol (or certain other substances herein classified as phenol equivalents), when reacted on with a phosphorus sulfur compound such as, for example, phosphorus-pentasulfide (P 8 become chemically transformed to what will herein be termed thiophospho-fatty acid compounds, which compounds are highly active as flotation collecting agents.

It is pointed out that in the above reaction the phenol or its equivalent is involved in the transformation of an unsaturated fatty acid substance to a thiophospho-fatty acid compound, said compound containing the phenols, etc. as a part of its molecular structure.

Although oleic acid has been indicated as preferred unsaturated fatty acid substance for preparing the flotation reagent of the present invention, other unsaturated fatty acids, (containing .422 carbon atoms), or

I mixtures of the same can also be employed,

such as, for example, crotonic acid, decylenic acid, undecylenic acid, elaidic acid, rapic acid, ricinoleic acid, linoleic acid, brassidic acid, eruic, etc.

Or instead of an unsaturated fatty acid the unsaturated fatty acid esters may be employed, suchras, for example, butyl oleate. Of interest also are the unsaturated fatty acid substances which consist essentially of glyceride esters of the unsaturated fatty acids such as, for example, olive oil, fish oils, cotton-seed oils, tung oil, etc. While these will function they are not as active as the unsat-' urated fatty acids.

Application filed February 19, 1931. Serial No. 517,126.

As phenol equivalents that may be employed in the preparation of the thiophos-- pho-fatty acid compounds of the present invention, we give the following classification I of compounds:

(a) Phenolic compounds, such as carbolic acid, cresols, xylenols, tar acids or closely related homologues of the same.

(b) The hydrogenated phenolic compounds. (0) The aliphatic alcohols, containing from one up to six carbon atoms such as, for example, ethyl alcohol, n-propyl alcohol, nbutyl alcohol, n-amyl alcohol, n-hexyl alcohol, as well as isomers of these alcohols. 85

(d) The aliphatic and aromatic mercaptols such as the ethyl, propyl, etc. mercaptols, phenyl mercaptol or closely related homologues of the same.

(6) The aliphatic and aromatic amines such as for example, ethyl amine, aniline, toluidine, alpha-naphthyl-amine or closely related homologues.

Bodies falling within the above classifica-- tion (a to e inclusive) include phenols and substances which are, in the present invention, equivalents of phenols. These sub-- stances may be referred to generically as a phenol-like substance, which term is hereinafter used in that sense.

It is understood that any mixtures of the above classified compounds may also be employed, such mixtures being considered as phenol equivalents and such mixtures are in-- cluded within the scope of the present invention.

The thiophospho-fatty acid compounds prepared b the reaction of P 8 on the unsaturated atty acid substance dissolved or mixed with a phenol or phenol equivalent,

constitute a class of flotation reagents that bonates, oxides, silicates, etc.

Itis not necessary that chemically ure substances be used in the preparation 0 the .100

above reagents, since unrefined products can be employed with metallurgical results practically as good as those obtained with pure chemlcals.

The following example is illustrative of the preparation of the flotation reagent of the present invention:

To a mixture of 50 parts of oleic acid and 50 arts of a phenol at 100 (1, 20 parts of P 5 are slowly added with stirring. After all of the P 8 has been added the reaction is continued for about three hours.

Working under substantially the same conditions, the phenol in the above preparation may be replaced with an equal weight (50 parts, or thereabout) of any ofthe various phenol equivalents listed above, or in place of oleic acid, other unsaturated fatty acid substances as above indicated may be employed. Phosphorus trisulfide may be used instead of the pentasulfide in the example given, being employed in equimolecular proportion under very much the same reaction conditions.

In the above preparation I do not limit myself to the reaction temperature given, nor to the proportion of reacting materials employed. In some cases a reaction temperature of 50 C., or thereabout, and a longer reaction period may advantageously be employed, while in other cases a temperature of 150 0., or thereabout, is preferable. It is conceivable that even lower or higher temperatures than those given may be more suitable for certain of these reactions.

Instead of carrying out the reaction as above indicated, the reaction may be carriedout in two steps, first the reaction of phenol (or its equivalent) with P 8 to form an organic thiophosphoric. acid, which is then comined with oleic acid, as the second step, to form a thiophospho-oleic acid compound. Either procedure yields substantially the same reaction product.

Without limiting the present invention to any'theory of reaction, it is believed that the reactions involved in the above type of preparation include first the formation of an intermediate organic thiophosphoric acid which then reacts with oleic acid, for exam le, at the double bond to form a thiophosp ooleic acid reaction product.

ere an unsaturated fatty acid is employed, ,as in the aboveexample, the reaction product may be reacted with an alkali or alaline earth hydroxide to form the alkali or alkaline earth metal salt of the thiophosphofatty acid compound, which with some ores may be a preferable reagent to the free acid compound.

In the froth flotati n of ores by the use of thei above products s collecting agents the said products, alth'ough possessing some frothing action, may require the use of a suitable frothing agent such as, for example,

ine oil, terpineol, cresylic acid or the like.-

he said reagents and frothing agents may obtained in many cases by the use of 0.1 to

0.2 pound per ton of ore.

The pulp is then subjected to the ordinary aeration or froth flotation operation, producing a foam carrying the mineral content from the ore. The flotation can be conducted in any type of froth flotation cell and in a neutral, alkaline or acid circuit, as desired.

In the use of an alkaline circuit it is sometimes preferable to add the alkali after the I above reagents have been added and thor-' onghly dispersed with the ore pulp.

, As illustrative of the practice of the invention 0.15 pound per ton of a thiophospho oleic acid compound (made by the reaction of oleic acid, pentasol (a mixture of isomeric alcohols containing 5 carbon atoms), and P S was employed in conjunction with the froth flotation of a difiicultly floatable copper bearing mineral (containing about 23% oxidized copper mineral) of the Phelps-Dodge Corporation, together with 0.1 pound of terpineol, an alkaline circuit being employed therewith. A recovery of 80%, or thereabout, of the copper bearing mineral was obtained, in the form of a good grade concentrate.

This same reagent when employed in conjunction with the flotation concentration of Utah Copper Co. ore, under substantially the same conditions, gave a recovery of better than of the copper bearing mineral together with a good grade of concentrate.

In the above tests the thiophospho-oleic acid reagent was first thoroughly dispersed with the ore pulp in a ball mill before adding the lime for alkalinity.

VVhat is claimed is:

1. A process which comprises floating ore material in the presence of a reaction product of a phosphorus sulfide on an 'unsatu-' 4. The froth flotation of metalliferous material while in the resence of a reaction product of a pho orus sulfide on oleic acid and a phenolike substance, as herein specified.

5. The froth flotation of metalliferous material while in the presence of a reaction product of a phosphorus sulfide on oleic acid and a tar acid, as herein specified.

6. The froth flotation of metalliferous material while in the presence of a reaction product of a phosphorus sulfide, on oleic acid and an alcohol, as herein specified.

7. The froth flotation of metalliferous material while in the presence of a reaction product of a phosphorus sulfide on oleic acid and pentasol, as herein specified.

8. The froth flotation of metalliferous material while in the presence of a reaction product of a phosphorus sulfide such on oleic acid and an organic amino compound, as herein specified.

9.'A new flotation reagent comprising a reaction product of a phosphorus sulfide on an unsaturated fatty acid substance and a phenol as herein specified.

10. A new chemical product comprising a reaction product of a phosphorus sulfide on an unsaturated fatty acid substance and a phenol as herein specified.

11. A process which comprises reacting with a phosphorus sulfur compound on an unsaturated fatty acid substance and a phenol to yield a thiophospho fatty acid compound of flotation value,'as herein specified.

12. In the art of froth flotation, the step of floating material to be concentrated in the presence of the herein described flotation.

a ent which comprises a reaction product 0% a phosphorus sulfide compound on an unsaturated fatty acid substance and a substance selected from the herein described group consisting of (a) phenolic compounds, b) the hydrogenated phenolic compounds, $0) the aliphatic alcohols containing from 1 to 6 carbon atoms, ((1), the aliphatic and aromatic mercaptols, and (e) the aliphatic and aromatic amines.

13. In the art of froth flotation the step 0 floating material to be concentrated in the presence of the herein described flotation agent which comprises a reaction product of a phosphorus sulfur compound on an un-' saturated fatty acid substance and a phenol.

14. In the art of froth flotationthe step of floating material to be concentrated in the presence of the herein described flotation agent which comprises an alkali-forming metalisalt and a thiophospho-fatty acid compoun p r 15. In the art of froth flotation the step of floating material to be concentrated in the prese cc of the herein described flotation agen which comprises a sodium salt of a thiophospho-fatty acid compound.

16. The froth flotation of ore material in the presence of a reaction (product of P 8, on an unsaturated fatty aci phenol-like substance.

17. The froth flotation of metalliferou material in the presence of a reaction roduct of P 8, on an unsaturated fatty and substance and a phenol-like substance.

substance and a,

18. In the art of froth flotation the step of floating material to be concentrated in the presence of the herein described flotation agent which comprises a reaction product of a phosphorus sulfur compound on an un-- saturated fatty acid substance and a phenollike substance.

In testimony whereof I have signed my name to this specification.

ORIN D. CUNNINGHAM.

CERTIFICATE OF CORRECTION.

Patent No. 1,902,838. Mareh28. 1933.

ORIN D. CUNNINGHAM.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as followsz Page 3, line 20, claim 8, strike out the word "such"; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 16th day of May, A. D. 1933.

M. J. Moore. (Seal Acting Commissioner of Patents. 

